CN103733311A - Thin film structures and devices with integrated light and heat blocking layers for laser patterning - Google Patents

Thin film structures and devices with integrated light and heat blocking layers for laser patterning Download PDF

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CN103733311A
CN103733311A CN201280038837.4A CN201280038837A CN103733311A CN 103733311 A CN103733311 A CN 103733311A CN 201280038837 A CN201280038837 A CN 201280038837A CN 103733311 A CN103733311 A CN 103733311A
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layer
device layer
laser
thermal barrier
patterning
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CN103733311B (en
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宋道英
冲·蒋
秉·圣·利奥·郭
约瑟夫·G·戈登
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Applied Materials Inc
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/02—Details
    • H01L31/0216—Coatings
    • H01L31/02161—Coatings for devices characterised by at least one potential jump barrier or surface barrier
    • H01L31/02162—Coatings for devices characterised by at least one potential jump barrier or surface barrier for filtering or shielding light, e.g. multicolour filters for photodetectors
    • H01L31/02164—Coatings for devices characterised by at least one potential jump barrier or surface barrier for filtering or shielding light, e.g. multicolour filters for photodetectors for shielding light, e.g. light blocking layers, cold shields for infrared detectors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/02—Details
    • H01L31/0216—Coatings
    • H01L31/02161—Coatings for devices characterised by at least one potential jump barrier or surface barrier
    • H01L31/02167—Coatings for devices characterised by at least one potential jump barrier or surface barrier for solar cells
    • H—ELECTRICITY
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    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/02—Details
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    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
    • H01L31/042—PV modules or arrays of single PV cells
    • H01L31/0445—PV modules or arrays of single PV cells including thin film solar cells, e.g. single thin film a-Si, CIS or CdTe solar cells
    • H01L31/046—PV modules composed of a plurality of thin film solar cells deposited on the same substrate
    • H01L31/0463—PV modules composed of a plurality of thin film solar cells deposited on the same substrate characterised by special patterning methods to connect the PV cells in a module, e.g. laser cutting of the conductive or active layers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/04—Construction or manufacture in general
    • H01M10/0404—Machines for assembling batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • H01M6/40—Printed batteries, e.g. thin film batteries
    • H—ELECTRICITY
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    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/02—Details
    • H01L31/0236—Special surface textures
    • H01L31/02366—Special surface textures of the substrate or of a layer on the substrate, e.g. textured ITO/glass substrate or superstrate, textured polymer layer on glass substrate
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    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
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    • H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
    • H01L31/1876—Particular processes or apparatus for batch treatment of the devices
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/04—Construction or manufacture in general
    • H01M10/0436—Small-sized flat cells or batteries for portable equipment
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H01M4/0471—Processes of manufacture in general involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Abstract

Selective removal of specified layers of thin film structures and devices, such as solar cells, electrochromics, and thin film batteries, by laser direct patterning is achieved by including heat and light blocking layers in the device/structure stack immediately adjacent to the specified layers which are to be removed by laser ablation. The light blocking layer is a layer of metal that absorbs or reflects a portion of the laser energy penetrating through the dielectric/semiconductor layers and the heat blocking layer is a conductive layer with thermal diffusivity low enough to reduce heat flow into underlying metal layer(s), such that the temperature of the underlying metal layer(s) does not reach the melting temperature Tm, or in some embodiments does not reach (Tm)/3, of the underlying metal layer(s) during laser direct patterning.

Description

There is membrane structure and device for the Integrated Light thermal barrier of laser patterning
the cross reference of related application
The U.S. Provisional Application the 61/521st that the application's request was filed an application on August 8th, 2011, the rights and interests of No. 212, are all incorporated to this application herein by reference.
The present invention is according to the W15P7T-10-C-H604 contract of being authorized by U.S. Department of Defense, under the support of U.S. government, makes.Government has some right in the present invention.
Technical field
Embodiments of the present invention relate to the maskless manufacturing process of membrane structure and device, relate in particular to the construction and device that comprises photo-thermal barrier layer for improvement of laser patterning.
Background technology
Be used for such as hull cell (thin film battery, TFB), electrochromism (electrochromic, EC) membrane structure of device, solar cell etc. and the laser technology of device are for from substrate front side (film side) the optionally various layers of ablation/line (scribe), leave some complete and be not damaged layer.For from metal selective laser ablation/line semiconductor/dielectric, due to the high thermal diffusion coefficient of metal, heat is delivered to lower metal from semiconductor/dielectric easily.Referring to Fig. 1 of the explanation of the estimation degree as thermal region 105, the laser ablation that wherein may occur to be caused by fixed laser bundle 101 damages---thermal region penetrating metal layer 103 and even extending in substrate/lower floor 104; Within the thermoisopleth 106 of estimating is illustrated in thermal region 105---thermoisopleth is not to calculate or measure to obtain, but laser damage degree based on observing is estimated.In addition, the penetrable semiconductor/dielectric of part laser 102 and enter metal 103, described part laser can be absorbed and further be increased by metal the temperature of metal.The temperature of lower metal can reach the evaporation point of described lower metal during the laser ablation of semiconductor/dielectric, and this can cause fusing and the vaporization of lower metal, and causes the function damage of film apparatus.For example, in TFB processes, may need to use the laser ablation from front side to remove dielectric layer to allow to form adhesive pad (bonding pad) on conduction current-collector (current collector) layer.Referring to Fig. 2 of diagram typical hull cell (TFB) stacking (stack), stacking substrate 201, cathode collector (the cathode current collector of comprising of described hull cell, CCC) 202, negative electrode (for example, LiCoO 2) 203, electrolyte (for example; LiPON) 204, anode (for example; Li, Si-Li and other interlayer oxides (intercalated oxide)) 205, anode collector (anode current collector, ACC) and protective finish 207.But, during the laser straight of TFB connects patterning, for example, for example, as electrolyte (, LiPON) and negative electrode (, LiCoO 2) while being removed by laser ablation, current collector layer (being generally the Ti/Au that is less than 1 micron) can reach the high temperature up to the evaporation point of current collector layer.This high temperature causes current-collector fusing or even vaporization, and high temperature inevitably reduces the charge/discharge efficiency of electric current collection efficiency and TFB entirety.
Significantly, have the needs of improving one's methods that connect patterning for the laser straight of TFB, EC and similar structures and device, described method is not damaged the function of the rest layers of membrane structure and device.
Summary of the invention
Conventionally, the maskless laser straight that the present invention relates to membrane structure and device connects patterning, described membrane structure and device are such as solar cell, electrochromic device and TFB, in described direct patterning, ablation need to stop and not affecting lower floor, the metal electric contact layer of for example TFB at designated layer place with high selectivity.According to the embodiment of the present invention, by laser straight, connecing patterning selectivity, to remove designated layer be to realize in stacking by photo-thermal barrier layer being included in to device/structure under the designated layer for the treatment of to be removed by ablation.(herein " ... below " be to define by the direction of laser beam---laser beam arrives barrier layer after passing designated layer first.) photoresist layer can be the metal level that has high-melting-point and have adequate thickness, to absorb and/or to reflect all laser that penetrate designated layer, and thermal barrier can be the conductive layer with enough low thermal diffusion coefficient, from most of heat of laser, be comprised in layer to be removed guaranteeing.The thickness on photo-thermal barrier layer and the thermal diffusion coefficient of thermal barrier can be designated to guarantee that the temperature of lower floor is kept the fusing point T lower than described lower floor during laser ablation process m.In addition, the thickness on photo-thermal barrier layer and the thermal diffusion coefficient of thermal barrier can be designated to guarantee that lower floor's temperature is kept lower than recrystallization temperature during laser ablation process---for normally (T of metal m)/3.In the situation that not affecting/damage lower metal layer, can be between metal level and dielectric or semiconductor layer, or even between different metal layer, realize selectivity, as long as photo-thermal barrier layer is incorporated between described metal level and dielectric or semiconductor layer.In some embodiments, photo-thermal barrier layer can be individual layer.In other embodiments, photoresist layer and the thermal barrier order in stacking can be put upside down.In addition, Ear Mucosa Treated by He Ne Laser Irradiation can be from substrate top or substrate below---and under latter event, laser is treated in arrival before the device layer of ablation/remove through substrate.
According to certain embodiments of the present invention, by laser beam and laser straight, connecing the film apparatus that patterning compatibility removes dielectric layer and/or semiconductor layer for selectivity can comprise: substrate; First device layer, described first device layer covers described substrate; The first thermal barrier, described the first thermal barrier covers described first device layer; The first photoresist layer, described the first photoresist layer covers described the first thermal barrier; With the second device layer, described the second device layer covers described the first photoresist layer; Wherein said the first photoresist layer is the metal level that absorbs or reflect a part of laser energy that arrives described the first photoresist layer, and described the first thermal barrier is the conductive layer with thermal diffusion coefficient D, described thermal diffusion coefficient D is enough low to reduce the heat that flows through described the first thermal barrier, makes the temperature of neighboring devices layer during laser straight connects patterning, exceed the fusion temperature T of described neighboring devices layer m.
According to further execution mode of the present invention, by laser beam laser straight, connecing the method that patterning film apparatus removes dielectric layer and/or semiconductor layer for selectivity can comprise: film apparatus as above is provided; Connect film apparatus described in patterning with laser straight, described laser beam is removed the Ear Mucosa Treated by He Ne Laser Irradiation part of described the second device layer, wherein said laser beam before arriving described the first photoresist layer through described the second device layer.Alternatively, or additionally, the Ear Mucosa Treated by He Ne Laser Irradiation part that laser straight connects patterning can remove described first device layer, wherein said laser beam passed described first device layer before arriving described the first thermal barrier.
This paper describes according to selective laser patterned tool of the present invention, and comprise the equipment of described selective laser patterned tool.
Accompanying drawing explanation
After the following description of reading by reference to the accompanying drawings the specific embodiment of the present invention, these and other aspect of the present invention and feature will be apparent for those skilled in the art, in described accompanying drawing:
Fig. 1 is the sectional view of the hierarchy (layered structure) that is exposed to laser beam during laser pattern metallization processes;
Fig. 2 is the sectional view of hull cell (TFB);
Fig. 3 be according to certain embodiments of the present invention during laser pattern metallization processes, there is the sectional view that is exposed to the photoresist layer of laser beam and the hierarchy of thermal barrier;
Fig. 4 is the sectional view of the hull cell with photoresist layer and thermal barrier (TFB) according to certain embodiments of the present invention;
Fig. 5 is the sectional view of the hull cell (TFB) with two photoresist layers and two thermal barrier according to certain embodiments of the present invention;
Fig. 6 is the hull cell with photoresist layer and thermal barrier (TFB) according to certain embodiments of the present invention and the sectional view that incides the structural laser beam of TFB by substrate;
Fig. 7 is the schematic diagram of selective laser patterned tool according to certain embodiments of the present invention;
Fig. 8 is the schematic diagram of the thin film deposition cluster tool of manufacturing for TFB according to certain embodiments of the present invention;
Fig. 9 is the representative graph of the thin film deposition system with multiple series connection (in-line) instrument of manufacturing for TFB according to certain embodiments of the present invention; With
Figure 10 is the representative graph of the series connection deposition tool of manufacturing for TFB according to certain embodiments of the present invention.
Embodiment
Now with reference to accompanying drawing, describe embodiments of the present invention in detail, described execution mode is provided as illustrative example of the present invention, to make those skilled in the art can put into practice the present invention.Significantly, the following drawings and example also do not mean that scope of the present invention be limited to single execution mode, but other execution modes are via exchanging some or all of describe or illustrated element is also possible.In addition, in the situation that some element of the present invention can be used known elements partially or even wholly to implement, will be only to being described for understanding necessary those parts of the present invention in described known elements, and by omission the detailed description of other parts to described known elements in order to avoid fuzzy the present invention.In this manual, the execution mode of the single parts of diagram should be considered as to restriction; More precisely, the invention is intended to contain other execution modes that comprise multiple same parts, and vice versa, unless clearly stated in addition in this article.In addition, applicant does not wish that any term in this specification or claimed scope is belonged to rare or special implication, sets forth unless made like this clearly.Further, the present and the future's of the known elements that explanation is mentioned in this article by way of example known equivalents is contained in the present invention.
Conventionally, the maskless laser straight that the present invention relates to membrane structure and device connects patterning, described membrane structure and device are such as solar cell, electrochromic device and TFB, in described direct patterning, ablation need to stop and not affecting lower floor, the metal electric contact layer of for example TFB at designated layer place with high selectivity.According to the embodiment of the present invention, by laser straight, connecing patterning selectivity, to remove designated layer be to realize in stacking by photo-thermal barrier layer being included in to device/structure under the designated layer for the treatment of to be removed by ablation.(herein " ... below " be to define by the direction of laser beam---laser beam arrives barrier layer after passing designated layer first.Referring to wherein photoresist layer 310 and thermal barrier 320, be integrated into device Fig. 3 in stacking.) photoresist layer can be the metal level with high melting temperature and adequate thickness, to absorb and/or to reflect all laser that penetrate designated layer; In addition, photoresist layer can have mirrored surface and maybe can have rough surface.Thermal barrier can be the layer with enough low thermal diffusion coefficient, is comprised in dielectric layer/semiconductor layer guaranteeing from most of heat of laser.The thickness on photo-thermal barrier layer and the thermal diffusion coefficient of thermal barrier can be designated to guarantee that the temperature of lower floor is kept the fusing point T lower than described lower floor during laser ablation process m.In addition, the thickness on photo-thermal barrier layer and the thermal diffusion coefficient of thermal barrier can be designated to guarantee that lower floor's temperature is kept lower than recrystallization temperature during laser ablation process---for normally (T of metal m)/3.In the situation that not affecting/damage lower metal layer, can be between metal level and dielectric or semiconductor layer, or even between different metal layer, realize selectivity, as long as photo-thermal barrier layer is incorporated between described metal level and dielectric or semiconductor layer.The comparative descriptions of Fig. 3 and Fig. 1 is for stoping thermal region 305 to extend to the function of the thermal barrier 320 of metal level 103.Thermoisopleth 306 in Fig. 3 shows the higher temperature gradient of the device in thermal barrier 320 within stacking; Described thermoisopleth is not to calculate or measure to obtain, but degree based on viewed laser damage is estimated.In some embodiments, photo-thermal barrier layer can be individual layer---for example individual layer thermoelectricity metal material.In other embodiments, photoresist layer and the thermal barrier order in stacking can be put upside down.Photo-thermal barrier layer can be integrated into stacking in, avoid simultaneously by stress or configuration of surface problem be incorporated into stacking in.In some embodiments, functional for what install, photoresist layer and thermal barrier must all be conducted electricity---for example, in TFB, when photoresist layer and thermal barrier be used in the CCC of device in stacking directly over time.
Fig. 4 provides photoresist layer 410 and thermal barrier 420 is incorporated in TFB for protect the example of cathode collector during laser patterning.Laser barrier layer 410 absorbs and/or reflects through the stacking all or most of laser of layer; described layer is stacking comprise following one or more: protective finish 207, anode collector (ACC) 206, anode 205, electrolyte 204 and negative electrode 203, and the heat that thermal barrier 320 is limited in stacking middle generation is diffused into cathode collector (CCC) 202 during stacking laser treatment.The material character on photo-thermal barrier layer and thickness are selected to keep the temperature of cathode collector lower than T mto avoid the fusing of CCC, and in some embodiments, selected to keep the temperature of cathode collector lower than recrystallization temperature, for metal, be approximately (T m)/3, to avoid CCC recrystallization during stacking laser ablation.In addition, in the time of compared with the TFB that there is no photo-thermal barrier layer with processing, because the energy content in stacking (concentration of heat) is larger, so the efficiency of laser ablation process increases.
In the example of the TFB of Fig. 4, photoresist layer 410 can be very thin metal level, and for example thickness is less than
Figure BDA0000464376790000051
golden film described in metal level can absorb and/or reflect the laser that penetrates stacking semiconductor/dielectric.Thermal barrier 420 can be thin (for nanosecond (nano-second) laser be conventionally greater than 1000 and be conventionally greater than for psec (pico-second) laser
Figure BDA0000464376790000062
) but there is the conductive layer of extremely low thermal diffusion coefficient, for example, thermal diffusion coefficient is 1.2x10 -2cm 2the ITO(tin indium oxide of/s) and thermal diffusion coefficient be 6.4x10 -2cm 2the titanium of/s.The thermal diffusion coefficient that it should be noted that thermal barrier is less than 0.1cm conventionally 2/ sand the thickness of thermal barrier conventionally close to or be greater than that diffusion length---diffusion length is given by √ (D τ), wherein τ is that laser pulse duration and D are the thermal diffusion coefficients of material.Photo-thermal barrier layer can be combined into one deck, as long as this layer is enough thick enough low to keep the temperature of CCC lower than T to absorb the most of laser and the thermal diffusion coefficient that are not reflected m, and in some embodiments lower than (T m)/3.For example, when picosecond laser is used to laser patterning,
Figure BDA0000464376790000063
thick titanium film can be used for photo-thermal barrier layer the two.
In some embodiments of the present invention, multipair photo-thermal barrier layer can be incorporated to structure or install stacking in.Fig. 5 diagram is incorporated to the example of TFB in stacking by two pairs of photo-thermal barrier layers.When photoresist layer 511 and thermal barrier 512 are used in laser patterning protective finish 207, protect semiconductor/dielectric stacking (layer 203,204,205 and 206), and photoresist layer 510 and thermal barrier 520 are used in laser patterning semiconductor/dielectric and protect CCC202 when stacking.Photo-thermal barrier layer can be placed between other layers of TFB, if have between the negative electrode of high-termal conductivity and electrolyte or be placed between the electrolyte and anode with high-termal conductivity although described photo-thermal barrier layer is placed in, may have the further requirement for some material character of coupling.It should be noted that every a pair of photo-thermal barrier layer can be used for producing different patterns when using more than a pair of photo-thermal barrier layer.
In the of the present invention further execution mode with photo-thermal barrier layer, for TFB, may need the punch die patterning (die patterning) by substrate, as shown in Figure 6.Laser 601 is to use from the back side of substrate---in other words, laser before arriving layer to be removed first through substrate---this need to have the substrate of suitable optical property (the low absorption under optical maser wavelength).For example, infrared ray IR (infrared, infrared) laser can be used for silicon substrate, if or substrate be glass, UV-VIS (ultraviolet-visible, ultraviolet-visible) laser can be used for from substrate-side punch die patterning so.Removing of " upper strata " is a kind of " blast (explosion) " technique, described technique " on " occur before the fusing of layer; Should " blast " technique only need a small amount of laser flux (fluence), for example, stacking for the typical TFB on glass substrate, laser flux is for being less than 1J/cm 2.In stacking shown in Fig. 6, the heat from laser in CCC202 may be enough to make CCC fusing and vaporization, remove from the layer of the CCC top of substrate and device stacking (described stackingly comprise layer 203,204,205,206 and 207, and photoresist layer 610 and thermal barrier 620) explosively.It should be noted that for this " blast " technique, photo-thermal barrier layer is also not always required, but in heat being concentrated on to the layer (being CCC in this example) below thermal barrier in thermal barrier, photo-thermal barrier layer can be helpful.Unless it should be noted that and take preventive measures, otherwise " blast " technique produced particle (particulate) and the melted material that may be deposited on device again.But, can develop Integrated Solution to alleviate potential deposition problems again.
In addition, some embodiments of the present invention comprise use single to photo-thermal barrier layer to produce two different patterns from stacking top with by substrate by Direct Laser patterning---the patterning by substrate is for defining the separator substrate, and from the patterning at stacking top stacking for above patterning photo-thermal barrier layer.May need different laser to produce two kinds of patterns.
(wherein laser passed substrate before arriving layer to be removed from the stacking method of the complete shielding layer of substrate regions to use laser, and the wherein stacking ground floor on substrate, the thermal barrier on ground floor and the photoresist layer on thermal barrier of being included in) can comprise: use laser beam from substrate backside illuminated layer stack region, laser beam penetrates ground floor by substrate, and wherein ground floor is ablated and the whole stacking substrate surface having passed through from laser of ground floor top is blown down.Photoresist layer is the metal level that absorbs or reflect the Part I laser energy that penetrates substrate and ground floor, and thermal barrier is the conductive layer with enough low thermal diffusion coefficient, to guarantee that the temperature of the ground floor on substrate exceedes the fusion temperature of described ground floor.
Conventional laser line or Color Laser Projection Technology can be used for selective laser Patternized technique of the present invention.The number of laser can be: one, for example, have the UV/VIS laser (by laser flux/dosage control selectivity) of picopulse width; Two, the combination (by optical maser wavelength/flux/dosage control selectivity) of for example UV/VIS and IR nanosecond and picosecond laser; Or multiple (by optical maser wavelength/flux/dosage control selectivity).The scan method of laser scribing system can be by galvanometric workbench (stage) motion, beam motion or described motion both.The diameter of laser facula (spot) size of laser scribing system can be adjusted to 1cm from 100 microns.At substrate place, for the laser area of laser projection system, can be 5mm 2or larger.In addition, can use other type of laser and configuration.
Fig. 7 is the schematic diagram of selective laser patterned tool 700 according to the embodiment of the present invention.Instrument 700 comprises the laser 701 for patterning apparatus 703 on substrate 704.In addition, also diagram is for passing through the laser 702 of substrate 704 patternings, although laser 701 can be used for by substrate 704 patternings (if substrate is reversed).Be provided for the substrate holder/workbench 705 of maintenance and/or moving substrate 704.Workbench 705 can have hole to hold the laser by substrate pattern.Instrument 700 can be arranged to substrate fixing during laser ablation, or mobile substrate---and laser 701/702 also can be fixing or movably; In some embodiments, substrate and laser can be movably, and in the case, this moves by control system and adjusts.The standalone version (stand-alone version) of instrument 700 is illustrated in Fig. 7, and described instrument comprises SMF and comprises glove box and front chamber.Execution mode shown in Fig. 7 is according to instrument of the present invention example---it is contemplated that many other configurations of this instrument, for example, glove box may be also inessential in the case of the TFB without lithium.In addition, instrument 700 can be arranged in the chamber with suitable environment, and described chamber is similar to the hothouse using as in lithium paper tinsel is manufactured.
Fig. 8 is the schematic diagram of the treatment system 800 for the manufacture of TFB device according to certain embodiments of the present invention.Treatment system 800 comprises SMIF (the standard mechanical interface that is connected to cluster tool, SMIF), described cluster tool is equipped with clean (the reactive plasma clean of reactive plasma, RPC) chamber and treatment chamber C1-C4, described cluster tool can be used in processing step as above.Also glove box can be attached to cluster tool.Glove box for example can be stored in substrate, in inert environments (, under the inert gas such as He, Ne or Ar), this after alkali metal/alkaline-earth metal deposition of great use.If need, also can use the front chamber that is connected to glove box---front chamber is gas heat exchanger chambers (inert gas is exchanged for air, and vice versa), and described chamber allows substrate to be passed turnover glove box, and does not pollute the inert environments in glove box.(it should be noted that glove box also can be had enough hothouse environment of low dew point and substitute, described enough low dew points are similarly used by Li Bo manufacturer.) cavity C 1-C4 can be arranged to the processing step of manufacturing hull cell device, described processing step for example can comprise: deposit described in TFB heap superimposition selective laser patterning as above stacking.The example of suitable cluster tool platform comprises the display cluster tool of AKT, such as the 10th generation display cluster tool or AppliedMaterial(Applied Materials) the Centura for less substrate tMand Endura tM.Although should be appreciated that and illustrate cluster arrangement for treatment system 1100, can utilize treatment chamber to be wherein arranged to a line and without the linear system of transmitting chamber, so that substrate moves to next chamber from a chamber continuously.
Fig. 9 illustrates the representative graph of the series system manufacturing system 500 with multiple series connection instruments 910,920,930 and 940 etc. according to certain embodiments of the present invention.Series connection instrument can comprise for depositing and the instrument of all layer of patterning TFB device.In addition, series connection instrument can comprise preconditioning and rear adjusting chamber.For example, instrument 910 can be substrate move through vacuum air lock (vacuum airlock) 915 to before in deposition tool 920 for setting up emptying (pump down) chamber of vacuum.The vacuum tool that some or all of series connection instruments can be separated by vacuum air lock 915.The order that it should be noted that process tool in process pipelines and given process instrument is determined the appointment TFB device producing method by being used---specify the instantiation of TFB device producing method to provide hereinbefore.In addition, substrate is removable by the series system manufacturing system of horizontal orientation or vertical orientation.In addition, selective laser patterning module also can be arranged to substrate fixing during laser ablation, or mobile substrate.
In order to describe substrate by the movement of all series system manufacturing systems as shown in Figure 9, in Figure 10, diagram only has the substrate conveyer belt 950 of a former bit serial instrument 910.The substrate holder 955(diagram substrate holder that contains substrate 1010 is partly cut so that substrate is visible) be installed on conveyer belt 950, or on the equivalent device of conveyer belt 950, for mobile retainer and substrate by series connection instrument 910, as shown in the figure.For the treatment of the suitable series connection platform of instrument 910, can be Applied Material(Applied Materials) Aton tMwith New Aristo tM.
The equipment that is used to form the electrochemical appliance such as hull cell according to the embodiment of the present invention can comprise: the first system, stacking for cover deposition (blanket depositing) on substrate, described stacking cathode collector layer, thermal barrier, photoresist layer, cathode layer, dielectric substrate, anode layer, anode collector layer and the protective finish of comprising; And second system, for stacking described in Direct Laser patterning.The first system can be the combination of cluster tool, series connection instrument, standalone tool or one or more above-mentioned instrument, and second system can be that standalone tool maybe can be integrated in the first system.Similar devices can be used for manufacturing solar energy equipment etc., and wherein the first system is configured to for depositing required stacking in specified device and photo-thermal barrier layer, and second system is for stacking described in Direct Laser patterning, as mentioned above.
Although the present invention describes in this article with reference to TFB, but instruction of the present invention and principle also may be used on improving one's methods for the manufacture of other membrane structures and device, described other membrane structures and device are such as solar cell and other electrochemical appliances such as electrochromic device, and wherein laser ablation need to stop and not affecting lower floor at designated layer place with high selectivity.
Although the present invention specifically describes with reference to some execution mode of the present invention, should it is evident that for those skilled in the art, can carry out the modifications and variations of form and details aspect in the situation that not deviating from the spirit and scope of the present invention.

Claims (15)

1. a film apparatus, described film apparatus connects patterning compatibility by laser beam and laser straight and removes dielectric layer and/or semiconductor layer for selectivity, and described film apparatus comprises:
Substrate;
First device layer, described first device layer covers described substrate;
The first thermal barrier, described the first thermal barrier covers described first device layer,
The first photoresist layer, described the first photoresist layer covers described the first thermal barrier; With
The second device layer, described the second device layer covers described the first photoresist layer;
Wherein said the first photoresist layer is the metal level that absorbs or reflect a part of laser energy that arrives described the first photoresist layer, and described the first thermal barrier is the conductive layer with thermal diffusion coefficient D, described thermal diffusion coefficient D is enough low to reduce the heat that flows through described the first thermal barrier, makes the temperature of neighboring devices layer during laser straight connects patterning, exceed the fusion temperature T of described neighboring devices layer m.
2. device as claimed in claim 1, wherein said neighboring devices layer is that described the second device layer and wherein said the first photoresist layer are to absorb described in a part that penetrates described the second device layer laser energy or the metal level towards described first device layer reflection by described described part laser energy, and described the first thermal barrier is the conductive layer with thermal diffusion coefficient D, described thermal diffusion coefficient D is enough low to reduce the heat that enters described first device layer from described the second device laminar flow, make the temperature of described first device layer during laser straight connects patterning, not reach the fusion temperature T of described first device layer m'.
3. device as claimed in claim 1, wherein said neighboring devices layer is that described first device layer and wherein said the first photoresist layer are to absorb to penetrate described in the part of described first device layer laser energy or the metal level towards described the second device layer reflection by described described part laser energy, and described the first thermal barrier is the conductive layer with thermal diffusion coefficient D, described thermal diffusion coefficient D is enough low to reduce the heat that enters described the second device layer from described first device laminar flow, make the temperature of described first device layer during laser straight connects patterning, exceed the fusion temperature T of described first device layer m'.
4. device as claimed in claim 1, wherein said the first thermal barrier is the conductive layer with enough low thermal diffusion coefficient, to reduce the heat that enters described first device layer from described the second device laminar flow, make the temperature of described first device layer during laser straight connects patterning, not reach (the T of described first device layer m)/3.
5. device as claimed in claim 1, wherein said the first photoresist layer and described the first thermal barrier are same layers.
6. device as claimed in claim 1, further comprises:
The second thermal barrier within described the second device layer and the second photoresist layer of described the second thermal barrier of covering;
The Part I that wherein said the second device layer comprises described the second device layer being covered by described the second thermal barrier and the Part II that covers the described second device layer of described the second photoresist layer, and wherein said the second photoresist layer is to absorb described in the part of the described Part II that penetrates described the second device layer laser energy or the metal level towards the described Part I reflection of described the second device layer by described described part laser energy, and described the second thermal barrier is the conductive layer with thermal diffusion coefficient D, described thermal diffusion coefficient D is enough low to reduce the heat that flows into the described Part I of described the second device layer from the described Part II of described the second device layer, make the temperature of the described Part I of described the second device layer during laser straight connects patterning, not reach the fusion temperature T of the described Part I of described the second device layer m".
7. device as claimed in claim 6; wherein said film apparatus is hull cell; described first device layer is that the described Part I of current collector layer and described the second device layer is stacking; describedly stackingly comprise anode collector, anode, electrolyte and negative electrode, and the described Part II of described the second device layer is protective finish.
8. device as claimed in claim 1, wherein said film apparatus is hull cell.
9. device as claimed in claim 8, wherein said first device layer is that current collector layer and described the second device layer are stacking, described stacking anode collector, anode, electrolyte and the negative electrode of comprising.
10. device as claimed in claim 8, wherein said the first photoresist layer is golden metal level, the thickness of the metal level of described gold is less than 10 nanometers.
11. devices as claimed in claim 8, wherein said the first thermal barrier is indium tin oxide layer.
12. 1 kinds of methods that connect patterning film apparatus and removed dielectric layer and/or semiconductor layer for selectivity by laser beam laser straight, comprise:
Film apparatus is provided, and described film apparatus comprises:
Substrate;
First device layer, described first device layer covers described substrate;
The first thermal barrier, described the first thermal barrier covers described first device layer,
The first photoresist layer, described the first photoresist layer covers described the first thermal barrier; With
The second device layer, described the second device layer covers described the first photoresist layer;
Wherein said the first photoresist layer is to absorb described in a part that penetrates described the second device layer laser energy or the metal level towards described first device layer reflection by described described part laser energy, and described the first thermal barrier is the conductive layer with thermal diffusion coefficient D, described thermal diffusion coefficient D is enough low to reduce the heat that enters described first device layer from described the second device laminar flow, makes the temperature of described first device layer during laser straight connects patterning, not reach the fusion temperature T of described first device layer m'; With
Laser straight connects film apparatus described in patterning, and described laser beam is removed the Ear Mucosa Treated by He Ne Laser Irradiation part of described the second device layer, wherein said laser beam before arriving described the first photoresist layer through described the second device layer.
13. methods as claimed in claim 12, wherein said film apparatus is further included in the second thermal barrier within described the second device layer and covers the second photoresist layer of described the second thermal barrier, and the Part I that wherein said the second device layer comprises described the second device layer being covered by described the second thermal barrier and the Part II that covers the described second device layer of described the second photoresist layer, and wherein said the second photoresist layer is to absorb described in the part of the described Part II that penetrates described the second device layer laser energy or the metal level towards the described Part I reflection of described the second device layer by described described part laser energy, and described the second thermal barrier is the conductive layer with thermal diffusion coefficient D, described thermal diffusion coefficient D is enough low to reduce the heat that flows into the described Part I of described the second device layer from the described Part II of described the second device layer, make the temperature of the described Part I of described the second device layer during laser straight connects patterning, not reach the described fusion temperature T of the described Part I of described the second device layer m", and wherein said laser straight connects the Ear Mucosa Treated by He Ne Laser Irradiation part that patterning further comprises the described Part II of removing described the second device layer.
14. 1 kinds of methods that connect patterning film apparatus and removed dielectric layer and/or semiconductor layer for selectivity by one or more laser beam laser straight, comprise:
Film apparatus is provided, and described film apparatus comprises:
Substrate;
First device layer, described first device layer covers described substrate;
The first thermal barrier, described the first thermal barrier covers described first device layer,
The first photoresist layer, described the first photoresist layer covers described the first thermal barrier; With
The second device layer, described the second device layer covers described the first photoresist layer;
Wherein said the first photoresist layer is to absorb the metal level reflecting towards described the second device layer from laser energy described in a part for the first laser beam penetrated bed or by described described part laser energy, and described the first thermal barrier has thermal diffusion coefficient D, described thermal diffusion coefficient D is enough low to reduce the heat that enters described the second device layer from described first device laminar flow, makes the temperature of described first device layer during connecing patterning with described the first laser beam laser straight, reach the fusion temperature T of described first device layer m'; With
Use described the first laser beam laser straight to connect film apparatus described in patterning, described laser straight map interlinking case is eliminated the Ear Mucosa Treated by He Ne Laser Irradiation part of described first device layer, wherein said the first laser beam passed described first device layer before arriving described the first thermal barrier, and wherein the each several part of described first thermal barrier, described first photoresist layer and the described second layer corresponding with the described illuminated portion of described first device layer is removed along with the removing of described illuminated portion of described first device layer.
15. methods as claimed in claim 14, further comprise: use the second laser beam laser straight to connect film apparatus described in patterning, described the second laser straight map interlinking case is eliminated the Ear Mucosa Treated by He Ne Laser Irradiation part of described the second device layer, wherein said the second laser beam installed layer through described second before arriving described the first photoresist layer, and wherein said the first photoresist layer is to absorb the metal level reflecting towards described first device layer from laser energy described in a part for described the second laser beam or by described described part laser energy that penetrates described the second device layer, described the first thermal barrier is the conductive layer with thermal diffusion coefficient D, described thermal diffusion coefficient D is enough low to reduce the heat that enters described first device layer from described the second device laminar flow, make the temperature of described first device layer during the laser straight that uses described the second laser beam connects patterning, not reach the fusion temperature T of described first device layer m'.
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